JP3089106B2 - Methanol production method - Google Patents
Methanol production methodInfo
- Publication number
- JP3089106B2 JP3089106B2 JP04192692A JP19269292A JP3089106B2 JP 3089106 B2 JP3089106 B2 JP 3089106B2 JP 04192692 A JP04192692 A JP 04192692A JP 19269292 A JP19269292 A JP 19269292A JP 3089106 B2 JP3089106 B2 JP 3089106B2
- Authority
- JP
- Japan
- Prior art keywords
- methanol
- carbon dioxide
- gas
- hydrogen
- mixture
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、メタノール製造方法に
関し、詳しくは、原料、特に二酸化炭素の損失が少な
く、二酸化炭素および水素より高選択率かつ高収率でメ
タノールを得ることが可能であって、例えば標識試薬な
どの製造に好適なメタノール製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing methanol, and more particularly, to a method for producing methanol with a high selectivity and a high yield over carbon dioxide and hydrogen with little loss of raw materials, particularly carbon dioxide. For example, the present invention relates to a method for producing methanol suitable for producing a labeling reagent and the like.
【０００２】[0002]
【従来の技術およびその課題】特開昭６０−１１４３７
号公報には、軽質炭化水素を水蒸気改質に付して、水
素、一酸化炭素および二酸化炭素に富む合成ガスとし、
この合成ガスをメタノール合成装置に送入してメタノー
ルを合成し、メタノールを冷却分離したあとの未反応ガ
スは、この合成ガスと共に合成装置に再循環せしめるメ
タノール製造の方法の改良について開示されているが、
再循環する未反応ガス中の水素は系外に放出する必要が
ある旨教示されており、未反応ガスの全量を反応装置に
再循環することについては記載されておらず、原料とし
て二酸化炭素および水素を使用すること、触媒としてＣ
ｕ−Ｚｎ−Ａｌ2 Ｏ3 系触媒を用いることなどについて
も記載されていない。特開昭６４−５００４３６号公報
には、一酸化炭素と二酸化炭素と水素とを含むガス状混
合物を、第１段階で、一定条件下、例えば５３重量％Ｃ
ｕＯと２７重量％ＺｎＯと８重量％Ａｌ2 Ｏ3 などより
なるＣｕ−ＺｎＯ−Ａｌ2 Ｏ3 系触媒の存在下に反応さ
せて得られるガス状混合物からメタノールと水を分離
し、分離されたガス状混合物を、ガス状混合物を循環す
る第２段階に送って同様に反応させ、得られた水および
メタノールを分離し、分離されたガス状混合物を二つの
部分に分割し、一方を第１段階から出てくるガス状混合
物と混合し、他の部分を反応系内へ循環することなく二
次成形炉へ送るメタノールの製造方法が記載されてい
る。しかしながら、特開昭６４−５００４３６号公報に
は原料として二酸化炭素および水素を用いること、反応
後のガス状混合物を全量反応系に再循環すること、など
については記載されていない。特開平３−１５１３３７
号公報には、疎水性メタノール合成触媒の存在下に、水
素と二酸化炭素、または水素と二酸化炭素と一酸化炭素
との混合物を反応させるアルコール、特にメタノールの
製造方法が開示されているが、得られるメタノールを分
離後、未反応ガスおよび副生ガスよりなるガス状混合物
を全量反応系に再循環させることは勿論、該ガス状混合
物を反応系に再循環させることについても具体的に記載
されていない。2. Description of the Related Art JP-A-60-11437
The publication discloses that light hydrocarbons are subjected to steam reforming to produce synthesis gas rich in hydrogen, carbon monoxide and carbon dioxide,
The synthesis gas is fed into a methanol synthesis device to synthesize methanol, and the unreacted gas after the methanol is cooled and separated is recirculated to the synthesis device together with the synthesis gas to improve the method of producing methanol. But,
It is taught that hydrogen in the unreacted gas to be recirculated needs to be released out of the system, and it is not described that the entire amount of unreacted gas is recirculated to the reactor. Use of hydrogen, C as catalyst
not described for such the use of u-Zn-Al 2 O 3 catalyst. JP-A-64-500436 discloses that in a first stage, a gaseous mixture containing carbon monoxide, carbon dioxide and hydrogen is mixed under a certain condition, for example, at 53% by weight of C.
The methanol and water are separated from the gaseous mixture obtained by reacting in the presence of uO and 27 wt% ZnO and 8 wt% Al 2 O 3 consisting of such as Cu-ZnO-Al 2 O 3 catalyst was separated The gaseous mixture is sent to a second stage in which the gaseous mixture is circulated and similarly reacted, the resulting water and methanol are separated, the separated gaseous mixture is divided into two parts, one of which is the first A process is described for the production of methanol which is mixed with the gaseous mixture emerging from the stage and sent to the forming furnace without recycling the other parts into the reaction system. However, JP-A-64-500436 does not disclose the use of carbon dioxide and hydrogen as raw materials, the recycle of the gaseous mixture after the reaction to the entire reaction system, and the like. JP-A-3-151337
The publication discloses a method for producing an alcohol, particularly methanol, in which hydrogen and carbon dioxide or a mixture of hydrogen, carbon dioxide and carbon monoxide are reacted in the presence of a hydrophobic methanol synthesis catalyst. It is specifically described not only to recycle the gaseous mixture consisting of the unreacted gas and the by-product gas after the methanol is separated, but also to recycle the gaseous mixture to the reaction system. Absent.
【０００３】本発明は、二酸化炭素および水素を原料と
して、原料、特に二酸化炭素の損失が少なく、高選択率
かつ高収率でメタノールを得ることが可能であって、例
えば標識試薬などの製造に好適なメタノール製造方法を
提供することを目的としている。According to the present invention, methanol can be obtained from carbon dioxide and hydrogen as raw materials with low loss of raw materials, particularly carbon dioxide, with high selectivity and high yield. An object of the present invention is to provide a suitable method for producing methanol.
【０００４】[0004]
【問題点を解決するための手段】本発明は、一定モル比
の二酸化炭素および水素よりなる原料混合ガスを、Ｃｕ
−Ｚｎ−Ａｌ2 Ｏ3 系触媒を充填した反応器に供給して
一定条件下に反応させ、得られたガス状反応混合物を気
液分離器を用いてメタノールおよび水よりなる液状混合
物と未反応ガスおよび副生ガスよりなるガス状混合物と
に分離し、該ガス状混合物を反応器に再循環し、液状混
合物よりメタノールを回収するメタノール製造方法にお
いて、該ガス状混合物の全量を反応器に再循環し、好ま
しくは、原料混合ガス中の二酸化炭素と水素とのモル比
を、化学量論的比率に対し、液状混合物に溶解し、分離
される二酸化炭素の量に見合うだけ二酸化炭素の比率を
加算してなるものとするか、あるいは液状混合物に溶解
し、分離される二酸化炭素を回収し、その全量を反応器
に再循環させると共に、原料混合ガス中の二酸化炭素と
水素とのモル比を実質上化学量論的比率とすることを特
徴とするメタノール製造方法を提供するものである。SUMMARY OF THE INVENTION According to the present invention, a raw material mixed gas consisting of carbon dioxide and hydrogen at a constant molar ratio
-Supply to a reactor filled with a Zn-Al 2 O 3 -based catalyst and react under a certain condition, and the resulting gaseous reaction mixture is unreacted with a liquid mixture composed of methanol and water using a gas-liquid separator. In a method for producing methanol in which a gaseous mixture consisting of gas and by-product gas is separated and the gaseous mixture is recycled to the reactor, and methanol is recovered from the liquid mixture, the entire amount of the gaseous mixture is recycled to the reactor. Circulating, preferably, the molar ratio of carbon dioxide and hydrogen in the raw material mixture gas is dissolved in the liquid mixture with respect to the stoichiometric ratio, and the ratio of carbon dioxide is adjusted to the amount of carbon dioxide to be separated and separated. Or by dissolving it in a liquid mixture, collecting the separated carbon dioxide, recirculating the entire amount to the reactor, and adjusting the molar ratio of carbon dioxide to hydrogen in the raw material mixed gas. There is provided a methanol production process, characterized in that the quality on the stoichiometric ratio.
【０００５】本発明方法の原料として用いられる二酸化
炭素および水素は、循環系における不活性ガスの蓄積を
防止するため、高純度のものを使用する必要がある。[0005] Carbon dioxide and hydrogen used as raw materials in the method of the present invention must be of high purity in order to prevent accumulation of inert gas in the circulation system.
【０００６】本発明において用いられる原料混合ガス中
の二酸化炭素と水素とのモル比は、通常水素対二酸化炭
素モル比として、２．７０〜３．０の範囲にあり、該モ
ル比が２．７０未満では反応系内に二酸化炭素が蓄積す
るため好ましくなく、該モル比が３．０を超えると反応
系内に水素が蓄積するため好ましくない。好ましくは、
原料混合ガス中の二酸化炭素と水素とのモル比は、化学
量論的比率に対し、液状混合物に溶解し、分離される二
酸化炭素の量に見合うだけ二酸化炭素の比率を加算して
なるものであり、具体的には水素対二酸化炭素モル比と
して２．８０〜２．９０の範囲にあり、それによって反
応系内の（水素／ＣＯ＋ＣＯ2 ）モル比を一定にして前
記ガス状混合物を反応器に全量再循環した場合でも連続
運転が可能となる。前記した、液状混合物に溶解し、分
離される二酸化炭素を回収し、その全量を反応器に再循
環する場合には、原料混合ガス中の二酸化炭素と水素と
のモル比を、実質上化学量論的比率とするのが特に好ま
しく、それによって、反応系内の（水素／ＣＯ＋Ｃ
Ｏ2 ）モル比を一定にして、前記ガス状混合物を反応器
に全量再循環した場合でも連続運転が可能となる。The molar ratio of carbon dioxide to hydrogen in the raw material mixed gas used in the present invention is usually in the range of 2.70 to 3.0 as a molar ratio of hydrogen to carbon dioxide, and the molar ratio is 2. If it is less than 70, carbon dioxide accumulates in the reaction system, which is not preferable. If the molar ratio exceeds 3.0, hydrogen accumulates in the reaction system, which is not preferable. Preferably,
The molar ratio of carbon dioxide to hydrogen in the raw material gas mixture is calculated by adding the ratio of carbon dioxide to the stoichiometric ratio as much as the amount of carbon dioxide dissolved and separated in the liquid mixture. And specifically, the molar ratio of hydrogen to carbon dioxide is in the range of 2.80 to 2.90, whereby the (hydrogen / CO + CO 2 ) molar ratio in the reaction system is kept constant and the gaseous mixture is reacted in the reactor. Even if the whole amount is recirculated, continuous operation becomes possible. When the carbon dioxide dissolved and separated in the liquid mixture is recovered and the whole amount is recycled to the reactor, the molar ratio between carbon dioxide and hydrogen in the raw material mixed gas is substantially stoichiometric. Stoichiometric ratios, whereby the (hydrogen / CO + C
Even when the gaseous mixture is completely recycled to the reactor with the O 2 ) molar ratio kept constant, continuous operation is possible.
【０００７】本発明において使用されるＣｕ−Ｚｎ−Ａ
ｌ2 Ｏ3 系触媒の例として、従来メタノールの水蒸気改
質用触媒として知られているもの、例えば東洋ＣＣＩ株
式会社製商品名ＭＤＣ−３があげられる。[0007] Cu-Zn-A used in the present invention
Examples of l 2 O 3 catalyst, those known as steam reforming catalyst of the prior art methanol, for example, Toyo CCI Co., Ltd. trade name MDC-3 and the like.
【０００８】本発明の反応器は、例えば流通式固定床を
用いることができる。In the reactor of the present invention, for example, a flow-type fixed bed can be used.
【０００９】本発明における反応は、通常反応温度２４
５〜３００℃、反応圧力３０〜１００ｋｇ／ｃｍ2 ・
Ｇ、Ｓ．Ｖ．１０００〜１００００ｈ-1の条件下に行な
われる。The reaction in the present invention is usually carried out at a reaction temperature of 24.
5 to 300 ° C, reaction pressure 30 to 100 kg / cm 2 ·
G, S. V. It is carried out under the condition of 1,000 to 10,000 h -1 .
【００１０】本発明において、反応器を出るガス状反応
混合物は、通常未反応ガスとしての二酸化炭素および水
素と副生ガスとしての一酸化炭素と反応生成物としての
メタノールおよび水とを含有する。該ガス状反応混合物
は、冷却後、気液分離器により、通常圧力８０〜９０ｋ
ｇ／ｃｍ2 ・Ｇ、温度−１０〜１０℃の条件下に、水お
よびメタノールとこれに溶解している二酸化炭素とより
なる液状混合物と、二酸化炭素および水素の未反応ガス
と副生ガスとしての一酸化炭素とよりなるガス状混合物
とに分離され、該ガス状混合物は全量反応器に再循環さ
れる。該液状混合物に溶解し、分離された二酸化炭素
は、好ましくは回収して反応器に再循環される。上記ガ
ス状混合物に含有される一酸化炭素の含有量は、原料と
して高純度の二酸化炭素および水素を用いること、特定
の触媒を用いること、原料混合ガス中の二酸化炭素と水
素とのモル比を特定すること、および前記ガス状混合物
の全量を反応器に再循環することにより一定値に保持さ
れ反応系内に蓄積されないことが見出され、特に原料混
合ガス中の二酸化炭素と水素とのモル比を特定して反応
系内の（水素／ＣＯ＋ＣＯ2 ）比を一定にすることによ
り、反応系内圧力がメタノール生成反応の反応率によら
ずに常時一定に保たれ、前記ガス状混合物を全量再循環
した場合でも連続運転が可能となる。In the present invention, the gaseous reaction mixture leaving the reactor usually contains carbon dioxide and hydrogen as unreacted gases, carbon monoxide as by-product gas, and methanol and water as reaction products. After cooling, the gaseous reaction mixture is usually subjected to a pressure of 80 to 90 k by a gas-liquid separator.
g / cm 2 · G, at a temperature of -10 to 10 ° C., as a liquid mixture of water and methanol and carbon dioxide dissolved therein, and as unreacted gas and by-product gas of carbon dioxide and hydrogen And a gaseous mixture consisting of carbon monoxide, the gaseous mixture being recycled to the reactor in its entirety. The carbon dioxide dissolved and separated in the liquid mixture is preferably recovered and recycled to the reactor. The content of carbon monoxide contained in the gaseous mixture is determined by using high-purity carbon dioxide and hydrogen as raw materials, using a specific catalyst, and a molar ratio of carbon dioxide and hydrogen in the raw material mixed gas. It was found that the gaseous mixture was maintained at a constant value and was not accumulated in the reaction system by recirculating the entire amount of the gaseous mixture to the reactor. By specifying the ratio and keeping the (hydrogen / CO + CO 2 ) ratio in the reaction system constant, the pressure in the reaction system is always kept constant irrespective of the reaction rate of the methanol production reaction, and the total amount of the gaseous mixture is reduced. Continuous operation is possible even in the case of recirculation.
【００１１】本発明方法において、反応を停止するに際
し、従来一般に行なわれているように反応系内の残存ガ
スを不活性ガスなどでパージすることなく、原料混合ガ
スの供給に代えて水素を供給し、前記と同様の条件下に
反応系内に残存するＣＯおよびＣＯ2 と反応させること
により、実質上その全量をメタノールに転化するのが好
ましい。In the method of the present invention, when the reaction is stopped, hydrogen is supplied instead of supplying the raw material mixed gas without purging the residual gas in the reaction system with an inert gas or the like as conventionally performed. However, it is preferable to convert substantially the entire amount to methanol by reacting with CO and CO 2 remaining in the reaction system under the same conditions as described above.
【００１２】本発明の第１の態様について、図１を参照
して以下説明する。所定の水素／ＣＯ2 モル比の原料混
合ガスを充填した原料タンク１から昇圧コンプレッサー
２により高圧タンク３に原料を昇圧する。この高圧タン
ク３内の圧力は常時反応系の圧力より高くなるよう昇圧
コンプレッサー２のオン−オフまたは回転数制御等の方
法で制御する。高圧タンク３内の混合原料ガスは２次圧
調整弁５により、反応系内の圧力が一定になるようにし
て反応循環系へ送られる。反応循環系に入った原料混合
ガスは、循環コンプレッサー１２によって循環されるガ
ス状混合物と共に反応器７へ送られ、メタノール合成反
応に供される。反応器７を出た反応混合ガスは冷却器８
により常温以下まで冷却され、生成したメタノール及び
水及び若干の副生物が液化され、気液分離器９に送られ
る。気液分離器９では液体のみが抜き出され、ガス状混
合物は全量が循環コンプレッサー１２によって反応器７
へ循環される。本発明の第２の態様について、図２を参
照して以下説明する。図１の液状混合物抜き出し口１３
から出る液状混合物を−１０〜１０℃および０〜１０ｋ
ｇ／ｃｍ2 ・Ｇ程度の条件下の低圧分離器１４において
フラッシュさせ、該液状混合物中に溶解していた二酸化
炭素を回収し、回収された二酸化炭素は昇圧コンプレッ
サー１６により昇圧されて反応器に循環される。これに
よりメタノールの収率をさらに高めることができる。The first embodiment of the present invention will be described below with reference to FIG. The raw material is pressurized from a raw material tank 1 filled with a raw material mixed gas having a predetermined hydrogen / CO 2 molar ratio to a high-pressure tank 3 by a high-pressure compressor 2. The pressure in the high-pressure tank 3 is controlled by a method such as turning on / off or controlling the number of rotations of the pressure-rising compressor 2 so that the pressure is always higher than the pressure of the reaction system. The mixed raw material gas in the high-pressure tank 3 is sent to the reaction circulation system by the secondary pressure control valve 5 so that the pressure in the reaction system becomes constant. The raw material mixed gas that has entered the reaction circulation system is sent to the reactor 7 together with the gaseous mixture circulated by the circulation compressor 12, and is subjected to a methanol synthesis reaction. The reaction mixture gas exiting the reactor 7 is cooled by a cooler 8
, The produced methanol and water and some by-products are liquefied and sent to the gas-liquid separator 9. In the gas-liquid separator 9, only the liquid is withdrawn, and the entire gaseous mixture is completely removed by the circulation compressor 12.
Circulated to The second embodiment of the present invention will be described below with reference to FIG. The liquid mixture outlet 13 of FIG.
-10 ~ 10 ° C and 0 ~ 10k
g / cm 2 · G, the mixture is flushed in the low-pressure separator 14 under the condition of about g / cm 2 · G, the carbon dioxide dissolved in the liquid mixture is recovered, and the recovered carbon dioxide is pressurized by the pressurizing compressor 16 and fed to the reactor. Circulated. This can further increase the yield of methanol.
【００１３】[0013]
【発明の効果】本発明によれば、二酸化炭素および水素
を原料として、原料、特に二酸化炭素の損失が少なく、
高選択率かつ高収率でメタノールを得ることが可能であ
って、例えば標識試薬などの製造に好適なメタノール製
造方法が提供される。According to the present invention, using carbon dioxide and hydrogen as raw materials, the loss of raw materials, particularly carbon dioxide, is small.
It is possible to obtain methanol with high selectivity and high yield, and a method for producing methanol suitable for producing, for example, a labeling reagent is provided.
【００１４】[0014]
【実施例】以下実施例により、本発明をさらに詳しく説
明する。The present invention will be described in more detail with reference to the following examples.
【００１５】実施例１ 図１に示した装置を用い、下記： 高圧タンク圧力 ：１１０ｋｇ／ｃｍ2 ・Ｇ 反応圧力 ： ９０ｋｇ／ｃｍ2 ・Ｇ 反応温度 ：２７０℃ ＳＶ ：９０００ｈ-1 冷却液化温度 ： −５℃ 原料（水素／二酸化炭素）モル比：２．８５ の条件下に、１０時間連続運転を行なったところ、定常
運転中の反応系内のガス組成は、ドライベースで、反応
器入口で水素７２．８容量％、二酸化炭素２５．６容量
％および一酸化炭素１．６容量％であり、循環ラインで
水素７２．１容量％、二酸化炭素２５．５容量％および
一酸化炭素２．４容量％であった。得られた生成物の含
有量は、メタノール４８．８モル％、水５１．２モル
％、エタノール０．００２４モル％、ギ酸メチル０．０
２７モル％およびホルムアルデヒド０．００２０モル％
であった。メタノールの選択率は９９．５％であり、メ
タノールの収率は二酸化炭素基準で９７．８％であっ
た。Example 1 Using the apparatus shown in FIG. 1, the following: High pressure tank pressure: 110 kg / cm 2 · G Reaction pressure: 90 kg / cm 2 · G Reaction temperature: 270 ° C. SV: 9000 h −1 Cooling liquefaction temperature: After continuous operation for 10 hours under the condition of a raw material (hydrogen / carbon dioxide) molar ratio of 2.85 at -5 ° C, the gas composition in the reaction system during the steady operation was on a dry basis at the reactor inlet. 72.8% by volume of hydrogen, 25.6% by volume of carbon dioxide and 1.6% by volume of carbon monoxide, and 72.1% by volume of hydrogen, 25.5% by volume of carbon dioxide and 2.4% by volume of carbon monoxide in the circulation line. % By volume. The content of the obtained product was as follows: methanol 48.8 mol%, water 51.2 mol%, ethanol 0.0024 mol%, methyl formate 0.0
27 mol% and formaldehyde 0.0020 mol%
Met. The selectivity for methanol was 99.5%, and the yield of methanol was 97.8% based on carbon dioxide.
【００１６】実施例２ 図１の装置を用い、実施例１と同様の条件下に５時間連
続運転を行なった後、運転停止時に原料混合ガスの供給
を停止すると同時に、原料混合ガスの代りに水素を供給
して、反応系内に残存するＣＯおよびＣＯ2 と反応させ
てメタノールに転化させた。この時の反応系内のガス組
成の循環ラインにおける経時変化を図３に示す。図３か
ら明らかなように、ＣＯ＋ＣＯ2 の濃度が０．５容量％
以下になるまで容易に反応が進行し、反応系内に残存す
るＣＯおよびＣＯ2 をほとんど無駄なくメタノールの製
造に利用できることがわかる。Example 2 After using the apparatus of FIG. 1 for continuous operation for 5 hours under the same conditions as in Example 1, when the operation was stopped, the supply of the raw material mixed gas was stopped, and instead of the raw material mixed gas, Hydrogen was supplied to react with CO and CO 2 remaining in the reaction system to convert it into methanol. FIG. 3 shows the change with time of the gas composition in the reaction system in the circulation line at this time. As is clear from FIG. 3, the concentration of CO + CO 2 is 0.5% by volume.
It can be seen that the reaction easily proceeds until the temperature becomes below, and that CO and CO 2 remaining in the reaction system can be used for producing methanol with little waste.
【図１】本発明の第１の態様を説明するためのフローチ
ャート図である。FIG. 1 is a flowchart for explaining a first embodiment of the present invention.
【図２】本発明の第２の態様を説明するためのフローチ
ャート図である。FIG. 2 is a flowchart for explaining a second embodiment of the present invention.
【図３】本発明の第３の態様を説明するためのグラフで
ある。FIG. 3 is a graph for explaining a third embodiment of the present invention.
１ 原料タンク ２ 昇圧コンプレッサー ３ 高圧タンク ４ 昇圧コンプレッサー制御用圧力センサー ５ ２次圧制御弁 ６ 混合容器 ７ 反応器 ８ 冷却器 ９ 気液分離器 １０ 液面制御弁 １１ 液面制御弁用液面センサー １２ 循環コンプレッサー １３ 液状混合物抜出し口 １４ 低圧気液分離器 １５ １次圧制御弁 １６ 昇圧コンプレッサー １７ 昇圧コンプレッサー制御用圧力センサー １８ 液状混合物抜出し口 DESCRIPTION OF SYMBOLS 1 Raw material tank 2 High-pressure compressor 3 High-pressure tank 4 High-pressure compressor control pressure sensor 5 Secondary pressure control valve 6 Mixing vessel 7 Reactor 8 Cooler 9 Gas-liquid separator 10 Liquid level control valve 11 Liquid level sensor for liquid level control valve 12 Circulating compressor 13 Liquid mixture discharge port 14 Low pressure gas-liquid separator 15 Primary pressure control valve 16 Boost compressor 17 Pressure sensor for boost compressor control 18 Liquid mixture discharge port
Claims (3)
なる原料混合ガスを、Ｃｕ−Ｚｎ−Ａｌ2 Ｏ3 系触媒を
充填した反応器に供給して一定条件下に反応させ、得ら
れたガス状反応混合物を気液分離器を用いてメタノール
および水よりなる液状混合物と未反応ガスおよび副生ガ
スよりなるガス状混合物とに分離し、該ガス状混合物を
反応器に再循環し、液状混合物よりメタノールを回収す
るメタノール製造方法において、原料混合ガス中の水素
対二酸化炭素モル比が、化学量論的比率に対し、液状混
合物に溶解し、分離される二酸化炭素の量に見合うだけ
二酸化炭素の比率を加算してなるように２．８０〜２．
９０の範囲にあって反応系内の水素と一酸化炭素および
二酸化炭素とのモル比を一定に保持した状態で該ガス状
混合物の全量を反応器に再循環することを特徴とするメ
タノール製造方法。1. A gas mixture obtained by supplying a raw material mixed gas comprising a fixed molar ratio of carbon dioxide and hydrogen to a reactor filled with a Cu—Zn—Al 2 O 3 catalyst and reacting under a predetermined condition. The gaseous reaction mixture is separated into a liquid mixture composed of methanol and water and a gaseous mixture composed of unreacted gas and by-product gas using a gas-liquid separator, and the gaseous mixture is recirculated to the reactor to form a liquid mixture. In the methanol production method for recovering more methanol , hydrogen in the raw material mixed gas
The molar ratio of carbon dioxide to stoichiometric
Dissolves in the mixture and only as much as the amount of carbon dioxide to be separated
2.80-2 to add the ratio of carbon dioxide.
Hydrogen and carbon monoxide in the reaction system in the range of 90 and
A method for producing methanol , wherein the entire amount of the gaseous mixture is recycled to a reactor while maintaining a constant molar ratio with carbon dioxide .
なる原料混合ガスを、Ｃｕ−Ｚｎ−Ａｌ2 Ｏ3 系触媒を
充填した反応器に供給して一定条件下に反応させ、得ら
れたガス状反応物を気液分離器を用いてメタノールおよ
び水よりなる液状混合物と未反応ガスおよび副生ガスよ
りなるガス状混合物とに分離し、該ガス状混合物を反応
器に再循環し、液状混合物よりメタノールを回収するメ
タノール製造方法において、原料混合ガス中の二酸化炭
素と水素とのモル比が実質上化学量論的比率にある状態
で、該ガス状混合物の全量と、該液状混合物に溶解し、
分離・回収される二酸化炭素の全量とを反応器に再循環
することを特徴とするメタノール製造方法。2. A gas mixture obtained by supplying a raw material mixed gas comprising a fixed molar ratio of carbon dioxide and hydrogen to a reactor filled with a Cu—Zn—Al 2 O 3 based catalyst and reacting under a predetermined condition. The gaseous reactant is separated into a liquid mixture composed of methanol and water and a gaseous mixture composed of unreacted gas and by-product gas using a gas-liquid separator, and the gaseous mixture is recirculated to the reactor to form a liquid mixture. In the methanol production method for recovering more methanol, the carbon dioxide
State in which the molar ratio of elemental to hydrogen is substantially stoichiometric
In, the total amount of the gaseous mixture and dissolved in the liquid mixture,
Recycle all the separated and recovered carbon dioxide to the reactor
A method for producing methanol.
代えて、水素を反応器に供給し、一定条件下に反応させ
て、反応系内に残存するＣＯおよびＣＯ2 を実質上全量
メタノールに転化させる請求項１または２記載のメタノ
ール製造方法。3. When the reaction is stopped, hydrogen is supplied to the reactor instead of the raw material mixed gas, and the reaction is carried out under a certain condition, so that CO and CO 2 remaining in the reaction system are substantially completely converted into methanol. The method for producing methanol according to claim 1 or 2 , wherein the methanol is converted.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP04192692A JP3089106B2 (en) | 1992-06-29 | 1992-06-29 | Methanol production method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP04192692A JP3089106B2 (en) | 1992-06-29 | 1992-06-29 | Methanol production method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06184023A JPH06184023A (en) | 1994-07-05 |
| JP3089106B2 true JP3089106B2 (en) | 2000-09-18 |
Family
ID=16295463
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP04192692A Expired - Fee Related JP3089106B2 (en) | 1992-06-29 | 1992-06-29 | Methanol production method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3089106B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101386564B (en) * | 2008-10-29 | 2011-12-28 | 西南化工研究设计院 | Technique for synthesizing methanol by hydrogen and carbon dioxide |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003040071A1 (en) * | 2001-11-06 | 2003-05-15 | Masayoshi Matsui | Method for hydrogenating carbon dioxide, treating apparatus, and basic material for hydrogenation |
| JP6930513B2 (en) * | 2018-10-24 | 2021-09-01 | Ｊｆｅスチール株式会社 | Organic matter synthesizer and synthesis method |
-
1992
- 1992-06-29 JP JP04192692A patent/JP3089106B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101386564B (en) * | 2008-10-29 | 2011-12-28 | 西南化工研究设计院 | Technique for synthesizing methanol by hydrogen and carbon dioxide |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06184023A (en) | 1994-07-05 |
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